EP0166695B1 - Process for the preparation of glycidyl thioethers - Google Patents

Process for the preparation of glycidyl thioethers Download PDF

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Publication number
EP0166695B1
EP0166695B1 EP85810291A EP85810291A EP0166695B1 EP 0166695 B1 EP0166695 B1 EP 0166695B1 EP 85810291 A EP85810291 A EP 85810291A EP 85810291 A EP85810291 A EP 85810291A EP 0166695 B1 EP0166695 B1 EP 0166695B1
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Prior art keywords
phase
atoms
alkyl
process according
epichlorohydrin
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EP85810291A
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German (de)
French (fr)
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EP0166695A3 (en
EP0166695A2 (en
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Hermann O. Dr. Wirth
Hans-Helmut Friedrich
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Novartis AG
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Ciba Geigy AG
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    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/24—Oxygen or sulfur atoms
    • C07D207/26—2-Pyrrolidones
    • C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D277/36—Sulfur atoms
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    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
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    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
    • C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
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    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/34—Compounds containing oxirane rings with hydrocarbon radicals, substituted by sulphur, selenium or tellurium atoms
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/20—Thiols; Sulfides; Polysulfides
    • C10M135/22—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M135/24—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof
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    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/20—Thiols; Sulfides; Polysulfides
    • C10M135/22—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M135/26—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing carboxyl groups; Derivatives thereof
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    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/20—Thiols; Sulfides; Polysulfides
    • C10M135/28—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring
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    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—Thio derivatives
    • C10M137/105—Thio derivatives not containing metal
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/084—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/085—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing carboxyl groups; Derivatives thereof
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/102—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon only in the ring
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
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Definitions

  • the present invention relates to a process for the preparation of glycidyl thioethers.
  • Glycidyl thioethers are compounds that play an important role in the synthesis of organic sulfur compounds, which are used, for example, as lubricant additives.
  • the present invention relates to a process for the preparation of glycidyl thioethers of the formula by reacting equivalent amounts of epichlorohydrin with a mercaptan of the formula II characterized in that R is a residue is where R 1 , R 2 and R 3 are independently C 1 ⁇ C 18 alkyl and together have no more than 22 C atoms and R 2 and R 3 are also hydrogen, or that RC 5 -C 6 cycloalkyl, is unsubstituted or substituted by C 1 ⁇ C 4 alkyl or phenyl or naphthyl, benzyl, furfuryl, or that R is mercaptoalkyl having 2 to 8 C atoms, which can optionally be interrupted by 1 or 2 ether O atoms, and that the reaction without an organic solvent in the presence of a base, by the phase transfer catalysis method, in contact with an aqueous phase using a phase transfer catalyst, is carried out at a temperature of from -30 ° C to
  • R represents a radical of the form is R 1- CH 2 -, or to act, wherein R 1 , R 2 and R 3 are each C 1 ⁇ C 18 alkyl.
  • C 1 -C 18 -alkyl are straight-chain or branched substituents, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, straight-chain or branched pentyl, Hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl.
  • R 1 , R 2 and R 3 together with the carbon atom to which they are attached form C 4 ⁇ C 20 alkyl, wherein none of these substituents R 1 , R 2 and R 3 may be hydrogen;
  • C 4 -C 16 alkyl is particularly preferred here, in particular tert-butyl, tert-nonyl (ex Phillips Petroleum) or tert-dodecyl is preferred, z.
  • tert.-Dodecyl should be understood to mean such a residue as described for tertiary dodecyl mercaptan in "Ulmanns Encyclopedia of Industrial Chemistry, 4th Edition, Volume 23, page 181-182, Verlag Chemie, Weinheim".
  • RC 5 -C 6 cycloalkyl is, it is cyclopentyl or cyclohexyl, preferably cyclohexyl.
  • R represents phenyl or naphthyl substituted by C 1 -C 4 -alkyl
  • phenyl or naphthyl can be substituted once to three times, but preferably once;
  • C 1 -C 4 -alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
  • R represents mercaptoalkyl with 2 to 8 carbon atoms, which may be replaced by 1 or 2 ether O- Atoms is interrupted, so it is simply substituted C 2 ⁇ C 8 mercaptoalkyl, the substitution by the SH group is possible in any position, but is preferably terminal, in particular it is -CH 2 -CH 2 -SH.
  • the process according to the invention is carried out in the presence of a base which is used in an equimolar amount or in slight excess with respect to the reactant mercaptan.
  • Suitable bases are e.g. B. alkali metal hydroxides such as sodium, potassium or lithium hydroxide or alkaline earth metal hydroxides such as calcium or magnesium hydroxide.
  • Alkali metal hydroxides are preferably used, in particular sodium hydroxide.
  • the inventive method is carried out in the presence of a phase transfer catalyst in a conventional amount, for. B. at least 0.6 wt .-% based on the amount of mercaptan and epichlorohydrin used.
  • phase transfer catalysts are various, such as z. B. are listed in CHEMTECH, February 1980, p. 111, Table 1, e.g. B. quaternary salts, polyethers, N-alkylphosphoramides.
  • Quaternary ammonium salts of the formula III are preferred in the process according to the invention wherein Ra, R b , Rc and R d are the same or different and straight-chain or branched alkyl radicals, where all 4 alkyl radicals together have 4 to 20 carbon atoms, or are benzyl and X ⁇ , Br ⁇ , Cl ⁇ , HSO 4 ⁇ or CH 3 SO 4 ⁇ is used.
  • Ra, Rb, R c and R d can mean the following alkyl radicals: z. B. methyl, isopropyl, n-butyl, sec.-butyl, tert.-butyl, tert.-amyl, 2-ethylhexyl, n-octyl, 1,1,3,3-tetramethylbutyl, n-dodecyl.
  • reaction partners in the process according to the invention are implemented at a temperature of -30 ° C. to 20 ° C., preferably at a temperature of 10-20 ° C., the maximum temperature not to be exceeded.
  • the phase separation is preferably carried out at elevated temperature.
  • a preferred embodiment of the process according to the invention consists in that the mercaptan of the formula II, epichlorohydrin and the phase transfer catalyst are introduced and a catalytic amount of an aqueous solution of the base is added at a temperature of less than 20 ° C. and then the base, reduced by the catalytic amount is added.
  • the process according to the invention is particularly preferred in the embodiment in which the mercaptan of the formula II and the phase transfer catalyst are introduced and epichlorohydrin and a catalytic amount of an aqueous solution of the base are added at a temperature of less than 20 ° C., and the base is then reduced by the catalytic amount is added.
  • Epichlorohydrin and the catalytic amount of base are preferably added separately but simultaneously.
  • the catalytic amount of base is approximately 2 to 5% of the total amount of base.
  • Examples of the glycidyl thioethers of the formula 1 which can be prepared by the process according to the invention are as follows: tert-octyl glycidyl thioethers n-octyl glycidyl thioethers tert.-Nonylglycidylthioether tert.-Dodecylglycidylthioether r n-Dodecylglycidylthioether tert.-Hexadecylglycidylthioether Cyclohexylglycidylthioether a-Naphthylglycidylthioether Benzylglycidylthioether furfurylglycidylthioethidethaneth by ether furfurylglycidylthioethidethaneth by ether Presence of a base, according to the phase transfer catalysis method, in contact with an aqueous
  • a mixture of 66 parts by weight of sodium hydroxide, 300 parts by weight of water and 8 parts by weight of tetrabutylammonium chloride is added to a mixture of 219 parts by weight of tert-octyl mercaptan and 135 parts by weight of epichlorohydrin at 15 to 20 ° C. with stirring and partial cooling (especially at the beginning of the addition) within 70 minutes dripped.
  • the reaction mixture is stirred at 50 ° C. for 1 hour, the aqueous phase is separated off, and the organic phase is washed with 200 parts by weight of water.

Abstract

1. A process for producing glycidyl thioethers of the formula I see diagramm : EP0166695,P6,F3 by reacting equimolar amounts of epichlorohydrin with a mercaptan of the formula II R-SH (II) wherein R is a radical see diagramm : EP0166695,P6,F5 in which R**1 , R**2 and R**3 independently of one another are each C1 -C18 alkyl and together have no more than 22 C atoms, and R**2 and R**3 are in addition hydrogen, or wherein R is C5 -C6 cycloalkyl, phenyl or naphthyl unsubstituted or substituted by C1 -C4 alkyl, or is benzyl or furfuryl, or wherein R is mercaptoalkyl which has 2 to 8 C atoms and can be interrupted by 1 or 2 ether-O atoms, and wherein the reaction is carried out at a temperature of -30 degrees C to +20 degrees C without organic solvent and in the presence of a base, by the phase-transfer catalysis process, in contact with an aqueous phase, a phase-transfer catalyst being employed.

Description

Die vorliegende Erfindung betriff ein Verfahren zur Herstellung von Glycidylthioethern.The present invention relates to a process for the preparation of glycidyl thioethers.

Glycidylthioether sind Verbindungen, die in der Synthese von organischen Schwefelverbindungen eine wichtige Rolle spielen, die beispielsweise als Schmierstoffadditive Verwendung finden.Glycidyl thioethers are compounds that play an important role in the synthesis of organic sulfur compounds, which are used, for example, as lubricant additives.

Die Herstellung von Glycidylthioethern ist an sich bekannt und in US-PS 2965652, US-PS 2731437, sowie in CA-PS 909793 beschrieben. Diese Verfahren verwenden Epichlorhydrin im Überschuss sowie organische Lösungsmittel, was in bezug auf gewerbehygienische und sicherheitstechnische Aspekte nicht unbedenklich ist. Ferner ist aus GB-PS 1 352527 und GB-PS 1359289 ein Verfahren bekannt, das ohne Epichlorhydrinüberschuss arbeitet, jedoch nur die Herstellung von S-Glycidyl-Verbindungen des Cyclododecans bzw. Cyclooctans beschreibt und wobei die angegebenen Ausbeuten auf diese Verbindungen beschränkt sind. Es wurde nun ein Verfahren gefunden, das diese Risikofaktoren nicht aufweist und zudem hohe Ausbeuten an Glycidylthioethern ergibt.The preparation of glycidyl thioethers is known per se and is described in US Pat. No. 2,965,652, US Pat. No. 2,731,437, and in CA Pat. No. 909793. These processes use epichlorohydrin in excess as well as organic solvents, which is not harmless in terms of industrial hygiene and safety-related aspects. Furthermore, from GB-PS 1 352527 and GB-PS 1359289 a process is known which works without excess epichlorohydrin, but only describes the preparation of S-glycidyl compounds of cyclododecane or cyclooctane and the yields given are limited to these compounds. A process has now been found which does not have these risk factors and which also gives high yields of glycidyl thioethers.

Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung von Glycidylthioethern der Formel

Figure imgb0001
durch Umsetzung von äquimalaren Mengen von Epichlorhydrin mit einem Mercaptan der Formel II
Figure imgb0002
dadurch gekennzeichnet, dass R ein Rest
Figure imgb0003
ist, worin Rl, R2 und R3 unabhängig voneinander C1―C18 Alkyl sind und zusammen nicht mehr als 22 C-Atome besitzen und R2 und R3 ausserdem Wasserstoff sind, oder dass R C5-C6-Cycloalkyl, unsubstituiertes oder durch C1―C4-Alkyl substituiertes Phenyl oder Naphthyl, Benzyl, Furfuryl ist, oder dass R Mercaptoalkyl mit 2 bis 8 C-Atomen bedeutet, das gegebenenfalls durch 1 oder 2 Ether-O-Atome unterbrochen sein kann, und dass die Umsetzung ohne organisches Lösungsmittel in Gegenwart einer Base, nach dem Phasentransfer-Katalyse-Verfahren, in Kontakt mit einer wässrigen Phase, wobei ein Phasentransfer-Katalysator eingesetzt wird, bei einer Temperaturvon -30°C bis +20°C ausgeführt wird. Stellt R ein Radikal der Form
Figure imgb0004
dar, so kann es sich um R1-CH2-,
Figure imgb0005
oder um
Figure imgb0006
handeln, wobei R1, R2 und R3 jeweils C1―C18-Alkyl, sind. Bei C1―C18-Alkyl handelt es sich um geradkettige oder verzweigte Substituenten, wie beispielsweise Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, sec.-Butyl, tert.-Butyl, geradkettiges oder verzweigtes Pentyl, Hexyl, Heptyl, Octyl, Nonyl, Decyl, Undecyl, Dodecyl, Tridecyl, Tetradecyl, Pentadecyl, Hexadecyl, Heptadecyl oder Octadecyl. Bevorzugt ist
Figure imgb0007
worin R1, R2 und R3 zusammen mit dem C-Atom, an das sie gebunden sind, C4―C20-Alkyl bilden, wobei keiner dieser Substituenten R1, R2 und R3 Wasserstoff sein darf; besonders bevorzugt ist hier nun C4―C16-Alkyl, insbesondere ist tert.-Butyl, tert.-Nonyl (ex Phillips Petroleum) oder tert.-Dodecyl bevorzugt, wobei z. B. unter tert.-Dodecyl solch ein Rest verstanden werden soll, wie er für tertiäres Dodecylmercaptan in «Ulmanns Enzyklopädie der technischen Chemie, 4. Auflage, Band 23, Seite 181-182, Verlag Chemie, Weinheim» beschrieben ist.The present invention relates to a process for the preparation of glycidyl thioethers of the formula
Figure imgb0001
 by reacting equivalent amounts of epichlorohydrin with a mercaptan of the formula II
Figure imgb0002
 characterized in that R is a residue
Figure imgb0003
 is where R 1 , R 2 and R 3 are independently C 1 ―C 18 alkyl and together have no more than 22 C atoms and R 2 and R 3 are also hydrogen, or that RC 5 -C 6 cycloalkyl, is unsubstituted or substituted by C 1 ―C 4 alkyl or phenyl or naphthyl, benzyl, furfuryl, or that R is mercaptoalkyl having 2 to 8 C atoms, which can optionally be interrupted by 1 or 2 ether O atoms, and that the reaction without an organic solvent in the presence of a base, by the phase transfer catalysis method, in contact with an aqueous phase using a phase transfer catalyst, is carried out at a temperature of from -30 ° C to + 20 ° C. R represents a radical of the form
Figure imgb0004
 is R 1- CH 2 -,
Figure imgb0005
 or to
Figure imgb0006
 act, wherein R 1 , R 2 and R 3 are each C 1 ―C 18 alkyl. C 1 -C 18 -alkyl are straight-chain or branched substituents, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, straight-chain or branched pentyl, Hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl. Is preferred
Figure imgb0007
 wherein R 1 , R 2 and R 3 together with the carbon atom to which they are attached form C 4 ―C 20 alkyl, wherein none of these substituents R 1 , R 2 and R 3 may be hydrogen; C 4 -C 16 alkyl is particularly preferred here, in particular tert-butyl, tert-nonyl (ex Phillips Petroleum) or tert-dodecyl is preferred, z. B. tert.-Dodecyl should be understood to mean such a residue as described for tertiary dodecyl mercaptan in "Ulmanns Encyclopedia of Industrial Chemistry, 4th Edition, Volume 23, page 181-182, Verlag Chemie, Weinheim".

Stellt R C5-C6-Cycloalkyl dar, so handelt es sich um Cyclopentyl oder Cyclohexyl, vorzugsweise Cyclohexyl.If RC 5 -C 6 cycloalkyl is, it is cyclopentyl or cyclohexyl, preferably cyclohexyl.

Stellt R durch Cl-C4-Alkyl substituiertes Phenyl oder Naphtyhl dar, so können Phenyl oder Naphthyl ein- bis dreifach, bevorzugt jedoch einfach, substituiert sein; bei Cl-C4-Alkyl handelt es sich um Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, sec.-Butyl oder tert.-Butyl.If R represents phenyl or naphthyl substituted by C 1 -C 4 -alkyl, then phenyl or naphthyl can be substituted once to three times, but preferably once; C 1 -C 4 -alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.

Stellt R Mercaptoalkyl mit 2 bis 8 C-Atomen dar, das gegebenenfalls durch 1 oder 2 Ether-O-Atome unterbrochen ist, so handelt es sich um einfach substituiertes C2―C8 Mercaptoalkyl, wobei die Substitution durch die SH-Gruppe in jeder Position möglich, vorzugsweise aber terminal ist, insbesondere handelt es sich um -CH2-CH2-SH.R represents mercaptoalkyl with 2 to 8 carbon atoms, which may be replaced by 1 or 2 ether O- Atoms is interrupted, so it is simply substituted C 2 ―C 8 mercaptoalkyl, the substitution by the SH group is possible in any position, but is preferably terminal, in particular it is -CH 2 -CH 2 -SH.

Bevorzugt werden nach dem erfindungsgemässen Verfahren Glycidylthioether der Formel I aus Epichlorhydrin und einem Mercaptan der Formel II hergestellt, worin R ein Radikal der Form

Figure imgb0008
ist, worin

  • R1, R2 und R3 unabhängig voneinander C1―C18 Alkyl sind und zusammen nicht mehr als 22 C-Atome besitzen und R2 und R3 ausserdem Wasserstoff sind, oder worin R Mercaptoalkyl mit 2 bis 8 C-Atomen ist, das gegebenenfalls durch 1 oder 2 Ether-O-Atome unterbrochen ist und die -SH-Gruppe terminal gebunden ist.
Glycidyl thioethers of the formula I are preferably prepared from epichlorohydrin and a mercaptan of the formula II by the process according to the invention, in which R is a radical of the form
Figure imgb0008
 is what
  • R 1 , R2 and R 3 are independently C 1 ―C 18 alkyl and together have no more than 22 C atoms and R 2 and R 3 are also hydrogen, or wherein R is mercaptoalkyl having 2 to 8 C atoms, that optionally interrupted by 1 or 2 ether O atoms and the -SH group is terminally bonded.

Besonders bevorzugt werden nach dem erfindungsgemässen Verfahren Glycidylthioether der Formel I durch Umsetzung von Epichlorhydrin mit einem Mercaptan der Formel II hergestellt, worin R ―CH2CH2―SH oder ein Radikal der Form

Figure imgb0009
ist, worin R!, R2 und R3

  • zusammen mit dem C-Atom, an das sie gebunden sind, C4―C20 Alkyl bilden, wobei keiner dieser Substituenten R!, R2 und R3 Wasserstoff sein darf.
Glycidyl thioethers of the formula I are particularly preferably prepared by reacting epichlorohydrin with a mercaptan of the formula II in which R ―CH 2 CH 2 ―SH or a radical of the form
Figure imgb0009
 is where R ! , R 2 and R3
  • together with the carbon atom to which they are attached form C 4 ―C 20 alkyl, none of these substituents R ! , R 2 and R 3 may be hydrogen.

Das erfindungsgemässe Verfahren wird in Gegenwart einer Base durchgeführt, die in bezug auf den Reaktionspartner Mercaptan in aequimolarer Menge oder leichtem Überschuss eingesetzt wird. Geeignete Basen sind z. B. Alkalihydroxide wie Natrium-, Kalium- oder Lithiumhydroxid oder Erdalkalihydroxide wie Calcium- oder Magnesiumhydroxid. Bevorzugt verwendet man als Base Alkalihydroxide insbesondere Natriumhydroxid.The process according to the invention is carried out in the presence of a base which is used in an equimolar amount or in slight excess with respect to the reactant mercaptan. Suitable bases are e.g. B. alkali metal hydroxides such as sodium, potassium or lithium hydroxide or alkaline earth metal hydroxides such as calcium or magnesium hydroxide. Alkali metal hydroxides are preferably used, in particular sodium hydroxide.

Das erfindungsgemässe Verfahren wird in Gegenwart eines Phasentransferkatalysators durchgeführt, der in üblicher Menge, z. B. mindestens 0,6 Gew.-% bezogen auf die eingesetzte Menge Mercaptan und Epichlorhydrin eingesetzt wird.The inventive method is carried out in the presence of a phase transfer catalyst in a conventional amount, for. B. at least 0.6 wt .-% based on the amount of mercaptan and epichlorohydrin used.

Als Phasentransferkatalysatoren eignen sich verschiedene, wie sie z. B. in CHEMTECH, Februar 1980, S. 111, Tabelle 1 aufgeführt sind, z. B. quaternäre Salze, Polyether, N-Alkylphosphoramide.As phase transfer catalysts are various, such as z. B. are listed in CHEMTECH, February 1980, p. 111, Table 1, e.g. B. quaternary salts, polyethers, N-alkylphosphoramides.

Bevorzugt werden im erfindungsgemässen Verfahren quaternäre Ammoniumsalze der Formel III

Figure imgb0010
worin Ra, Rb, Rc und Rd gleich oder verschieden sind und geradkettige oder verzweigte Alkylreste, wobei alle 4 Alkylreste zusammen 4 bis 20 C-Atome besitzen, oder Benzyl bedeuten und X⊖, Br⊖, Cl⊖, HSO4⊖ oder CH3SO4⊖ darstellt, eingesetzt.Quaternary ammonium salts of the formula III are preferred in the process according to the invention
Figure imgb0010
 wherein Ra, R b , Rc and R d are the same or different and straight-chain or branched alkyl radicals, where all 4 alkyl radicals together have 4 to 20 carbon atoms, or are benzyl and X⊖, Br⊖, Cl⊖, HSO 4 ⊖ or CH 3 SO 4 ⊖ is used.

Ra, Rb, Rc und Rd können folgende Alkylreste bedeuten: z. B. Methyl, iso-Propyl, n-Butyl, sec.-Butyl, tert.-Butyl, tert.-Amyl, 2-Ethylhexyl, n-Octyl, 1,1,3,3-Tetramethylbutyl, n-Dodecyl.Ra, Rb, R c and R d can mean the following alkyl radicals: z. B. methyl, isopropyl, n-butyl, sec.-butyl, tert.-butyl, tert.-amyl, 2-ethylhexyl, n-octyl, 1,1,3,3-tetramethylbutyl, n-dodecyl.

Besonders bevorzugt werden als Phasentransferkatalysator (n―C4H9)4NCl und (n―C4H9)4NBr, insbesondere (n―C4H9)4NBr, eingesetzt.Particular preference is given to using (n ― C 4 H 9 ) 4 NCl and (n ― C 4 H 9 ) 4 NBr, in particular (n ― C 4 H 9 ) 4 NBr, as the phase transfer catalyst.

Die Umsetzung der Reaktionspartner im erfindungsgemässen Verfahren erfolgt bei einer Temperatur von -30°C bis 20°C, vorzugsweise bei einer Temperatur von 10-20°C, wobei die Maximaltemperatur nicht überschritten werden soll.The reaction partners in the process according to the invention are implemented at a temperature of -30 ° C. to 20 ° C., preferably at a temperature of 10-20 ° C., the maximum temperature not to be exceeded.

Die Phasentrennung erfolgt für viskose Reaktionsprodukte vorzugsweise bei erhöhter Temperatur.For viscous reaction products, the phase separation is preferably carried out at elevated temperature.

Eine bevorzugte Ausführungsform des erfindungsgemässen Verfahrens besteht darin, dass das Mercaptan der Formel II, Epichlorhydrin sowie der Phasentransferkatalysator vorgelegt werden und bei einer Temperatur von weniger als 20°C eine katalytische Menge einer wässrigen Lösung der Base zugegeben wird und anschliessend die Base, vermindert um die katalytische Menge, zugegeben wird.A preferred embodiment of the process according to the invention consists in that the mercaptan of the formula II, epichlorohydrin and the phase transfer catalyst are introduced and a catalytic amount of an aqueous solution of the base is added at a temperature of less than 20 ° C. and then the base, reduced by the catalytic amount is added.

Besonders bevorzugt wird das erfindungsgemässe Verfahren in der Ausführungsform, worin das Mercaptan der Formel II und der Phasentransferkatalysator vorgelegt werden und bei einer Temperatur von weniger als 20°C Epichlorhydrin und eine katalytische Menge einer wässrigen Lösung der Base zugegeben werden und anschliessend die Base, vermindert um die katalytische Menge, zugegeben wird.The process according to the invention is particularly preferred in the embodiment in which the mercaptan of the formula II and the phase transfer catalyst are introduced and epichlorohydrin and a catalytic amount of an aqueous solution of the base are added at a temperature of less than 20 ° C., and the base is then reduced by the catalytic amount is added.

Vorzugsweise werden Epichlorhydrin und die katalytische Menge an Base getrennt aber gleichzeitig zugegeben.Epichlorohydrin and the catalytic amount of base are preferably added separately but simultaneously.

Die katalytische Menge an Base beträgt ungefähr 2 bis 5% der Gesamt-Menge an Base.The catalytic amount of base is approximately 2 to 5% of the total amount of base.

Es ist möglich, das erfindungsgemässe Verfahren zu automatisieren, z. B. die Epichlorhydrin-Zugabe durch Temperaturmessung und die Basen-Zugabe durch pH-Messung.It is possible to automate the method according to the invention, e.g. B. the epichlorohydrin addition by temperature measurement and the base addition by pH measurement.

Beispiele für die nach dem erfindungsgemässen Verfahren herstellbaren Glycidylthioether der Formel 1 sind folgende: tert.-Octylglycidylthioether n-Octylglycidylthioether tert.-Nonylglycidylthioether tert.-Dodecylglycidylthioether r n-Dodecylglycidylthioether tert.-Hexadecylglycidylthioether Cyclohexylglycidylthioether a-Naphthylglycidylthioether Benzylglycidylthioether Furfurylglycidylthioether Ethylen-diglycidylthioether, hergestellt durch Umsetzung von 2 Molen Epichlorhydrin mit einem Mol Dimercaptoethan nach dem erfindungsgemässen Verfahren, demnach dass die Umsetzung ohne organisches Lösungsmittel in Gegenwart einer Base, nach dem Phasentransferkatalyse-Verfahren, in Kontakt mit einer wässrigen Phase, wobei ein Phasentransferkatalysator eingesetzt wird, bei einer Temperatur von -30°C bis +20°C ausgeführt wird.Examples of the glycidyl thioethers of the formula 1 which can be prepared by the process according to the invention are as follows: tert-octyl glycidyl thioethers n-octyl glycidyl thioethers tert.-Nonylglycidylthioether tert.-Dodecylglycidylthioether r n-Dodecylglycidylthioether tert.-Hexadecylglycidylthioether Cyclohexylglycidylthioether a-Naphthylglycidylthioether Benzylglycidylthioether furfurylglycidylthioethidethaneth by ether furfurylglycidylthioethidethaneth by ether Presence of a base, according to the phase transfer catalysis method, in contact with an aqueous phase, using a phase transfer catalyst, is carried out at a temperature of -30 ° C to + 20 ° C.

Beispiel 1: tert-OctylglycidylthioetherExample 1: tert-Octylglycidylthioether

Zu einer Mischung aus 219 Gewichtsteilen tert-Octylmercaptan und 135 Gewichtsteilen Epichlorhydrin wird bei 15 bis 20°C unter Rühren und teilweiser Kühlung (besonders am Anfang der Zugabe) eine Lösung aus 66 Gewichtsteilen Natriumhydroxid, 300 Gewichtsteilen Wasser und 8 Gewichtsteilen Tetrabutylammoniumchlorid innerhalb von 70 Minuten zugetropft. Das Reaktionsgemisch wird 1 Stunde bei 50°C nachgerührt, die wässrige Phase wird abgetrennt, und die organische Phase wird mit 200 Gewichtsteilen Wasser gewaschen. Schliesslich wird dann die organische Phase im Vakuum destilliert, und man erhält den tert-Octylglycidylthioether als farblose Flüssigkeit mit einem Siedepunkt von 74 bis 75°C bei 0,02 Torr und einem Brechungsindex von n20 = 1,4803; die Ausbeute beträgt 250 Gewichtsteile, was 82% der theoretischen Ausbeute entspricht.A mixture of 66 parts by weight of sodium hydroxide, 300 parts by weight of water and 8 parts by weight of tetrabutylammonium chloride is added to a mixture of 219 parts by weight of tert-octyl mercaptan and 135 parts by weight of epichlorohydrin at 15 to 20 ° C. with stirring and partial cooling (especially at the beginning of the addition) within 70 minutes dripped. The reaction mixture is stirred at 50 ° C. for 1 hour, the aqueous phase is separated off, and the organic phase is washed with 200 parts by weight of water. Finally, the organic phase is then distilled in vacuo, and the tert-octylglycidylthioether is obtained as a colorless liquid with a boiling point of 74 to 75 ° C. at 0.02 Torr and a refractive index of n2 0 = 1.4803; the yield is 250 parts by weight, which corresponds to 82% of the theoretical yield.

Beispiel 2: tert-NonylglycidylthioätherExample 2: tert-Nonylglycidylthioether

In einem 1 1 Sovirel-Reaktor (doppelwandiges Reaktionsgefäss) mit Thermometer, Rührer, Dosiertropftrichter und Rückflusskühler wird 321 g tert-Nonylmercaptan, 184 g Epichlorhydrin und 4 g Tetrabutylammoniumchlorid vorgelegt. Zu dieser Lösung wird unter Rühren und intensiver Wasserkühlung 30 ml einer 22%igen wässrigen Natriumhydroxidlösung innerhalb 45 Minuten, und nach Abklingen der exothermen Reaktion nochmals 285 ml 22%ige Natriumhydroxidlösung innerhalb 60 Minuten, bei 15-20°C zugetropft. Das Reaktionsgemisch wird 30 Minuten bei 50°C nachgerührt, die wässrige Phase abgetrennt, die organische Phase 2 mal mit je 200 g Wasser gewaschen und die organische Phase im Vakuum getrocknet. Rückstand: 422 g (ber. 433 g) n

Figure imgb0011
: 1,4813; It. NMR enthält der Rückstand 92 Gew.-% tert-Nonylglycidylthioäther.321 g of tert-nonyl mercaptan, 184 g of epichlorohydrin and 4 g of tetrabutylammonium chloride are placed in a 1 1 Sovirel reactor (double-walled reaction vessel) with a thermometer, stirrer, metering dropping funnel and reflux condenser. 30 ml of a 22% aqueous sodium hydroxide solution are added dropwise to this solution with stirring and intensive water cooling within 45 minutes, and after the exothermic reaction has subsided, another 285 ml of 22% sodium hydroxide solution are added dropwise at 15-20 ° C. within 60 minutes. The reaction mixture is stirred at 50 ° C. for 30 minutes, the aqueous phase is separated off, the organic phase is washed twice with 200 g of water each time and the organic phase is dried in vacuo. Residue: 422 g (calc. 433 g) n
Figure imgb0011
: 1.4813; According to NMR, the residue contains 92% by weight of tert-nonylglycidylthioether.

Beispiel 3: n-OctylglycidylthioätherExample 3: n-octylglycidylthioether

In einem 1 I Sovirel-Reaktor (doppelwandiges Reaktionsgefäss) mit Thermometer, Rührer, Tropftrichter, Dosiertropftrichter und pH-Elektrode wird 293 g n-Octylmercaptan und 5 g Tetrabutylammoniumchlorid vorgelegt. Zu dieser Lösung wird unter intensiver Wasserkühlung und Rühren 184 g Epichlorhydrin innerhalb 80 Minuten bei einem pH-Wert von 11,6-12,0 eingetropft. Der pH-Wert wird durch entsprechende Dosierung von ca. 10 ml 22%iger wässriger Natriumhydroxidlösung über den gesamten Zeitraum von 80 Minuten konstant gehalten. Die Reaktionstemperatur sollte 20°C nicht übersteigen. Nach beendeter exothermer Reaktion wird 305 ml 22%ige Natriumhydroxidlösung innerhalb 15 Minuten eingetropft, das Reaktionsgemisch 30 Minuten bei 50°C nachgerührt, die wässrige Phase abgetrennt, die organische Phase 2 mal mit je 200 g Wasser gewaschen und die organische Phase im Vakuum fraktioniert. Die Ausbeute beträgt 382 g (94% d.Th.) mit einem Siedepunkt von 92-94°C bei 0,04 Torr mit einem Brechungsindex von n

Figure imgb0011
: 1,4718.293 g of n-octyl mercaptan and 5 g of tetrabutylammonium chloride are placed in a 1 liter Sovirel reactor (double-walled reaction vessel) with a thermometer, stirrer, dropping funnel, metering dropping funnel and pH electrode. 184 g of epichlorohydrin are added dropwise to this solution over the course of 80 minutes at a pH of 11.6-12.0, with intensive water cooling and stirring. The pH value is kept constant over the entire period of 80 minutes by appropriate dosing of about 10 ml of 22% aqueous sodium hydroxide solution. The reaction temperature should not exceed 20 ° C. After the exothermic reaction has ended, 305 ml of 22% sodium hydroxide solution are added dropwise within 15 minutes, the reaction mixture is subsequently stirred at 50 ° C. for 30 minutes, the aqueous phase is separated off, the organic phase is washed twice with 200 g of water each time and the organic phase is fractionated in vacuo. The yield is 382 g (94% of theory) with a boiling point of 92-94 ° C at 0.04 Torr with a refractive index of n
Figure imgb0011
: 1.4718.

Die folgenden Glycidylthioether wurden analog zu den in den Beispielen 2 und 3 beschriebenen Verfahren hergestellt.

Figure imgb0013
Figure imgb0014
 The following glycidyl thioethers were prepared analogously to the processes described in Examples 2 and 3.
Figure imgb0013
Figure imgb0014

Claims (9)

1. A process for producing glycidyl thioethers ofthe formula I
Figure imgb0021
by reacting equimolar amounts of epichlorohydrin with a mercaptan of the formula II
Figure imgb0022
wherein R is a radical
Figure imgb0023
in which R', R2 and R3 independently of one another are each C1―C18alkyl and together have no more than 22 C atoms, and R2 and R3 are in addition hydrogen, or wherein R is C5―C6cycloalkyl, phenyl or naphthyl unsubstituted or substituted by C1-C4alkyl, or is benzyl or furfuryl, or wherein R is mercaptoalkyl which has 2 to 8 C atoms and can be interrupted by 1 or 2 ether-O atoms, and wherein the reaction is carried out at a temperature of -30°C to +20°C without organic solvent and in the presence of a base, by the phase-transfer catalysis process, in contact with an aqueous phase, a phase-transfer catalyst being employed.
2. A process according to claim 1, wherein R ist a radical of the form
Figure imgb0024
in which R', R2 and R3 independently of one another are each C1―C18alkyl, and together have not more than 22 C atoms, and R2 and R3 are in addition hydrogen, or in which R is mercaptoalkyl which has 2 to 8 C atoms and can be interrupted by 1 or 2 ether-O atoms, and the -SH group is bound in the terminal position.
3. A process according to claim 1, wherein R is ―CH2―CH2―SH or a radical of the form
Figure imgb0025
in which R', R2 and R3 together with the C atom to which they are bound form C4―C20alkyl, where none of these substituents R1, R2 and R3 may be hydrogen.
4. A process according to claim 1, wherein the base used is an alkali metal hydroxide or an alkaline earth metal hydroxide.
5. A process according to claim 1, wherein the phase-transfer catalyst is a quaternary ammonium salt of the formula III
Figure imgb0026
in which Ra, Rb, Rc and Rd are identical or different, and are straight-chain or branched-chain alkyl radicals, all 4 alkyl radicals together having 4 to 20 C atoms, or are benzyl, and X⊖ is BrO, Cl⊖, HSO4⊖ or CH3SO4⊖.
6. A process according to claim 1, wherein the phase-transfer catalyst is used in an amount of at least 0.6% by weight, relative to the employed amount of mercaptan and epichlorohydrin.
7. A process according to claim 1, wherein the mercaptan of the formula II, epichlorohydrin and the phase-transfer catalyst are placed into the reaction vessel and, at a temperature of less than 20°C, a catalytic remainder of the base is added.
8. A process according to claim 1, wherein the mercaptan of the formula II and the phase-transfer catalyst are placed into the reaction vessel and, at a temperature of less than 20 °C, epichlorohydrin and a catalytic amount of an aqueous solution of the base are added, and subsequently the remainder of the base is added.
9. A process for producing ethylenediglycidyl thioethers by reacting 2 moles of epichlorohydrin with 1 mole of dimercaptoethane, wherein the reaction is carried out at a temperature of -30°C to +20°C without organic solvent and in the presence of a base, by the phase-transfer catalysis process, in contact with an aqueous phase, a phase-transfer catalyst being employed.
EP85810291A 1984-06-29 1985-06-24 Process for the preparation of glycidyl thioethers Expired EP0166695B1 (en)

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US4931576A (en) 1990-06-05
DE3573778D1 (en) 1989-11-23
EP0166695A3 (en) 1986-11-20
EP0166695A2 (en) 1986-01-02
JPS6124583A (en) 1986-02-03
CA1261861A (en) 1989-09-26
JPH06769B2 (en) 1994-01-05

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